Textile assistants



u A -F United States Patent TEXTILE ASSISTAN TS Bertram J. Garceau, Lincoln, R. I., assignor to Arnold, Hoffman & Co., Incorporated, Providence, R. L, a corporation of Rhode Island N Drawing. Application February 24, 1953, Serial No. 338,621

7 Claims. (Cl. 260-4045) The present invention relates to novel textile assistants and, more particularly, to improvements in the condensation products described in U. S. Patent No. 2,804,369, issued to Morgan, et al. on December '8, 1942.

The above mentioned U. S. Patent No. 2,304,369 describes the production of textile assistants by reacting a carbamyl derivative, such as urea, with the condensation product of an aliphatic polyamine and a fatty acid, acid ester or acid chloride. The products thus obtained are suitable for a variety of uses in the treatment of textile materials, e. g., as softening, wetting, lubricating, antistatic or water-proofing agents and offer the advantage over generally similar textile assistants of being relatively resistant to yellowing on storage or when heated after application to fabrics. However, it has now been found that, despite their improved resistance to yellow ing, these products still tend to yellow or become scorched when exposed to relatively high temperatures, for instance, temperatures in the neighborhood of about 135 to 210 C. This difliculty is particularly apparent in the treatment of .some of the more recently developed synthetic fibres, such as nylon, Orlon and Dacron, which require processing within the temperature range recited above.

The principal object of the present invention is to prcvide a novel group of condensation products suitable for application to textile materials for softening, lubricating and like purposes.

A more specific object of the invention is the provision of novel textile assistants which possess improved resistance to yellowing and scorching.

A further object of the invention is the provision of improvements in the condensation products described in U. S. Patent No. 2,304,369.

Another object of the invention is. to provide a group of textile assistants particularly adapted for application of synthetic fibres which normally require relatively high processing temperatures.

Still further objects and the entire scope of applicability of the present invention will become apparent from the detailed description given hereinafter; it should be understood, however, that the detailed description and specific examples, While indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.

The foregoing objects are accomplished, according to the present invention, by virtue of the discovery that the tendency of the condensation or reaction products, described inU. S. Patent No. 2,304,369, to yellow or become scorched on heating to temperatures of 185 to 210 C. or higher, can be virtually eliminated by further condensing, one or more of these reaction products with from 2 to mols of ethylene oxide, per mol of reaction product, followed by, if desired, solubilization of the resulting condensate with a suitable acid or alkylating agent.

According to the present invention, the non-yellowing characteristics of any of the condensation products described in U. S. Patent No. 2,304,369, and hereinafter referred to as amido condensation products to distinguish from the condensation products of the invention, can be improved by further condensation with ethylene oxide in the proportions stated, i. e., 2 to 15 mols ethylene oxide per mol of amido condensation product. Specifically, the amido condensation products proposed for reaction with ethylene oxide in this invention are substituted ureas, thioureas, guanidines, biurets, guanyl ureas, or diguanid-ines of high molecular weight, in which each of the terminal carbamyl nitrogens has been substituted through linkage with a polyamino acid amide.

These compounds are readily prepared in the manner indicated in U. S. Patent No. 2,304,669, by reacting the carbamyl derivatives, such as urea, thiourea, guanidine salts, biuret, diguanidiue, or guanyl urea with the condensation products secured from aliphatic polyamines and acids. These acids may be condensed with any of the aliphatic polyamines or substituted polyamines, such as ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, hexa methylene diam-inc, hydroxy ethyl ethylene diamine, ethyl ethylene diamine, 2, 2-dimethyl-1,3, diamino propane, 1,3, diamino isopropanol, beta beta diamino diethyl ether, and beta beta diamino diethyl thioether.

While the invention herein described is broadly applicable to the amido condensation products described in U. 5'. Patent No. 2,304,369, it has been found that particularly desirable reaction products are obtained by condensing one mol of the amido condensation product derived from two mols stearic acid, 2 mols aminoethylethanolamine and one mol of urea, with from 2 to 15 mols of ethylene oxide, and thereafter solubilizing the resulting condensate by reacting same with from 0:25 to one mol of ethyl acid phosphate. Such products, and especially the product obtained using 10 mols ethylene oxide, demonstrate outstanding softening and antistatic properties. on synthetic fibres while having the additional property of being unusually resistant to yellowing and scorching due to heat.

Another specific ethylene oxide reaction product which has been found to possess a resistance to scorching or yellowing remarkably'superior to the condensation product from which it is derived is that obtained by condensing the amido condensation product described in the preceding paragraph with two mols of ethylene oxide followed by solubilization of the resulting condensate with acetic acid.

Condensation according to the invention can be carried out in any convenient way using widely varying reaction conditions. Generally, however, condensation is effected by heat-ing the ethylene oxide and amido condensation product to a temperature of between 50 and 150 C., and preferably C. Condensation is usually completed within about 2 to 20 hours, although theexact time involved depends upon other operating conditions, e. g., nature of the amido condensation product being reacted, quantity of ethylene oxide utilized and condensation temperature.

The condensates obtained as a result of the condensation with ethylene oxide, according to'the invention, are. in many cases, directly soluble, or readily dispersible, in water. Such products as are water soluble or water dispersible are suitable without further treatment for application to textile fibres, as described, for example, in U. S. Patent No. 2,304,113, to soften, wet, lubricate or otherwise improve the characteristics of the fibres. In all cases, however, the ethylene oxide condensation products can be treated with appropriate solubilizing or alkylating agents to improve their water solubility prior to use. Such solubilization treatment can be carried out with any suitable acid, such as acetic, lactic, boric, oxalic, benzoic, salicyclic, furoic, citric, tartaric, formic, phthalic, succinic, or alkyl naphthalene sulphonic acids, or with an alkylating agent, such as ethyl acidphosphate, ethyl chloride, benzyl chloride, ethylene chlorohydrin, or dimethyl sulphate.

Solubilization can be effectively carried out at temperatures within the range of 80 to 140 C., using the solubilizing acids or alkylating agents referred to above in quantities of from about 0.2 to 1.0 mols per mol of condensation product being treated. it is also possible to use corresponding amounts of ethylene oxide in lieu of the, other agentsmentioned for solubilizing purposes, although it will be appreciated that such use of ethylene oxide is critically different from condensation thereof with the amido condensation products of U. S. Patent No. 2,304,369, as described herein.

The invention as above described is further illustrated, but not limited, by the following examples in which the quantities stated are in parts by weight.

Example 1 65 parts (about .08 mol) of the resinous or amido condensation product derived from stearic acid, aminoethylethanolamine and urea, in the manner described below, were heated in a still under vacuum at 100 C. for two hours and then cooled to 75 C.

Thereafter 37 /2 parts (.8 mol) ethylene oxide were slowly charged into the still and reaction between the resinous condensate and ethylene oxide permitted to go.

to completion at a temperature of 75 C. The reaction was completed in 15 hours, yielding 103 parts of ethylene oxide condensation product.

The ethylene oxide condensation product thus obtained was alkylated with .02 mols of ethyl acid phosphate. The thus solubilized product was applied in aqueous solution to nylon fabric which was thereafter exposed to heat treatment at a temperature of about 200 C. After this treatment, it was found that the fabric was not discolored whereas nylon fabric which was similarly treated with the amido condensation product used as starting material and exposed to 200 C. showed a definite yellow discoloration.

The fabric treated with the condensation products of the invention also demonstrated the following improved characteristics when compared with the conventionally treated fabric: softer, better lubricant, and better antistatic properties.

The amido condensation product used above for reaction with ethylene oxide corresponds with the product described in Example 8 of U. S. Patent No. 2,304,369, and was prepared according to the procedure set forth in that example, using two mols stearic acid, two mols aminoethylethanolamiue or hydroxyethyl ethylene diamine and one mol of urea.

Example 2 762 parts (1 mol) of the condensate of 2 mols of oleic acid with 2 mols of aminoethylethanolamine and 1 mol of urea was heated to 117 C. and 195 parts (4.4 mols) ethylene oxide gas fed into the system over a period of 8 hours during which the temperature reached 129' C. yielding 957 parts of ethylene oxide condensation product. The condensate so obtained was reacted with 126 parts (1 mol) ethyl acid phosphate.

The thus solubilized product when applied to cellulose acetate fabric from an aqueous solution resulted in a finish of superior antistatic properties and lubricity.

Example 3 65 parts (about .08 mol) of the amido condensation product of 2 mols stearic acid, 2 mols aminoethylethanolamine and 1 mol of urea were heated to 110 C. under vacuum for 1 hour.

Thereafter 7.5 parts (about 0.16 mol) ethylene oxide were slowly charged into the still and the reaction held at C. at 25 lbs. pressure for 2 hours yielding 72.5 parts of ethylene oxide condensation product.

The ethylene oxide product so obtained was reacted with 4.8 parts (.08 mol) acetic acid. The thus solubilized product was applied to cotton fabric from an aqueous solution. The fabric thus finished possessed greater resistance to yellowing due to heat than the same type of fabric treated in a like manner with the corresponding amido condensation product from which it was made. Substantially equivalent results were obtained using condensation products obtained by reacting 4, 6, 8, 10 and 15 mols of ethylene oxide with a mol of the above mentioned amido condensation product.

For the purpose of the present invention, it is essential that from 2 to 15 mols of ethylene oxide be utilized for each mol of amido condensation product utilized. That is to say, if the proportion of ethylene oxide utilized exceeds or is lower than that designated above, it has been found that the improved characteristics of the present products are not realized. Specifically, when using less than 2 mols of ethylene oxide per mol of amido condensation product there is substantially no improvement in the non-yellowing characteristics of the resulting products when heated on fabric whereas, when using substantially more than 15 mols of ethylene oxide per mol of amido product, the desirable softening and lubrieating properties of the present products are lost.

It will be appreciated that the invention is not limited to the specific condensation products described in the foregoing examples and is, instead, applicable for the purpose of improving the resistance to heat and other characteristics of all of the condensation products described in U. S. Patent No. 2,304,369. It will also be understood that, while the products of the invention are of particular value for treating synthetic fibres, such as nylon, which require processing at relatively high temperatures, these products may also be used with advantage in treating other textile fibres and materials, such as cotton, wool, linen, cellulose acetate and viscose, due to their desirable and, in some cases improved, softening and lubricating characteristics. Other advantages of the present products are increased solubility in water and compatibility with commonly used resin finishes and improved resistance to electrolytes.

Various modifications can be made in the invention as above described without deviating from the scope thereof as defined in the following claims.

Having described my invention, what I intend to claim as new is:

1. A textile assistant possessing improved resistance to yellowing, said assistant comprising the condensate obtained by heating together from 4 to 15 mols of ethylene oxide and one mol of an amido condensation product selected from the group consisting of carbamyl compounds and acid salts thereof having the general formula:

selected from the group consisting of hydrogen, a simple alkyl of less than five carbons, and an alkylol of less than 1* five carbons, and in which R3 and R4 may further represent a second acid polyamide chain, and in which general formula the carbamyl groups D1 and D2 represent a material selected from the group consisting of oxygen, sulfur, and imido groups, the number of such groups being as g ranges from 0 to 3 while in the side chains the letter A represents a material selected from the group consisting of amino(NH)--, a simple alkyl substituted amino of less than five carbons, an alkylol substituted amino of less than five carbons, oxygen, and sulfur; and the integers and j vary from 1 to 6, while e and l vary from O to 6, and m and t vary from 1 to 6.

2. A textile assistant as claimed in claim 1 wherein the amido condensation product of the stated formula is obtained from urea, a fatty acid and an aliphatic polyamine.

3. A textile assistant as claimed in claim 1 comprising the condensate obtained by heating together 10 mols of ethylene oxide and one mol of an amido condensation product of the stated formula, said amido condensation product being obtained from stearic acid, aminoethylethanolamine and urea.

4. A water-soluble textile assistant comprising the condensate of claim 3 solubilized by heating with ethyl acid phosphate.

5. The process for producing a textile assistant as claimed in claim 1 which comprises condensing by heating together from 4 to 15 mols of ethylene oxide and one mol of an amido condensation product having the formula stated in claim 1.

6. A process as claimed in claim 5 wherein the resulting condensate is solubilized by heating with a watersolubilizing compound selected from the group consisting of acids and alkylating agents.

7. Textile material treated with a textile assistant as claimed in claim 1.

References (Jited in the file of this patent UNITED STATES PATENTS 2,304,113 Morgan et al. Dec. 8, 1942 20 2,304,369 Morgan et al. Dec. 8, 1942 2,478,859 Carnes et al. Aug. 9, 1949 

1. A TEXTILE ASSISTANT POSSESSING IMPROVED RESISTANCE TO YELLOWING, SAID ASSISTANT COMPRISING THE CONDENSATE OBTAINED BY HEATING TOGETHER FROM 4 TO 15 MOLS OF ETHYLENE OXIDE AND ONE MOL OF AN AMIDO CONDENSATION PRODUCT SELECTED FROM THE GROUP CONSISTING OF CARBAMYL COMPOUNDS AND ACID SALTS THEREOF HAVING THE GENERAL FORMULA: 